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  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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  • B01D53/34—Chemical or biological purification of waste gases
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  • B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
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  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
  • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J20/28078—Pore diameter
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
  • B01J20/3204—Inorganic carriers, supports or substrates
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
  • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
  • B01J20/3234—Inorganic material layers
  • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/34—Regenerating or reactivating
  • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/42—Materials comprising a mixture of inorganic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2220/00—Aspects relating to sorbent materials
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  • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/48—Sorbents characterised by the starting material used for their preparation
  • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

Definitions

• the present invention relates to a process for the preparation of a solid mass for the capture of mercury containing an inorganic support and copper at least in part in the sulphide state, as well as a process for the regeneration of this solid mass.
• the present invention also relates to a process for preparing a precursor of a solid mass for capturing mercury.
• the solid masses prepared according to the present invention can be called indifferently absorption, capture, extraction or trapping masses.
• US-A-4094777 describes a process for the preparation of a mass for the capture of mercury comprising the incorporation of a copper compound into an inorganic support, followed by sulfurization at a temperature below 300 ° C.
• Sulfurization according to the process described in this patent is carried out using a gaseous agent, for example hydrogen sulfide, or a solution of an inorganic sulfide in water or in an organic solvent, by example an aqueous solution of sodium sulfide, potassium sulfide or ammonium sulfide.
• a gaseous agent for example hydrogen sulfide, or a solution of an inorganic sulfide in water or in an organic solvent, by example an aqueous solution of sodium sulfide, potassium sulfide or ammonium sulfide.
• H 2 S gaseous hydrogen sulphide
• sulphide solutions for example aqueous solutions of ammonium sulphide
• aqueous solutions of ammonium sulphide makes it possible to work at a relatively low temperature, for example between zero and one hundred degrees Celsius.
• ammonium sulfide is a toxic and easily decomposable compound, which complicates its use.
• the mercury capture efficiency of the masses obtained by this process decreases over time and their lifespan is limited.
• Said sulfurizing agent incorporated at least partially into the mineral support, preferably at least partially in its porosity, makes it possible to obtain a precursor of a solid mass for capturing mercury.
• Said precursor is then treated in a non-oxidizing atmosphere, for example neutral or reducing, and preferably neutral, usually under gas sweeping, at a temperature and for a time sufficient to allow the formation of copper sulfide and possibly sulfide of other metals. present when the mineral support contains it.
• the solid mineral supports or dispersants are usually chosen from the group formed by carbon, activated carbon, coke, silica, silicon carbide, silica gel, synthetic or natural silicates, clays, diatomaceous earths , fuller's earth, kaolin, bauxite, refractory inorganic oxides such as for example alumina, titanium oxide, zirconia, magnesia, silica-aluminas, silica-magnesia and silica-zirconia , alumina-boron oxide mixtures, aluminates, silico-aluminates, crystalline, synthetic or natural zeolitic aluminosilicates, for example mordenites, faujasites, offretites, erionites, ferrierites, zeolites ZSM5 and ZSM11, mazzites, and cements such as by example Secar type produced by Lafarge.
• refractory inorganic oxides such as for example alumina, titanium oxide, zirc
• Use is preferably made of a support chosen from the group formed by carbon, activated carbon, coke, silica, aluminas, silica-aluminas, silicates, aluminates and silico-aluminates.
• the support is chosen from the group formed by silica, aluminas, silica-aluminas, silicates, aluminates and silico-aluminates and alumina is very advantageously used.
• the mercury capture masses are intended to be used in the treatment of charges containing condensable hydrocarbons (for example C 4 or higher than C 4 ) at a temperature situated in the temperature range at which the capture takes place, found that the masses having an average pore diameter at least equal to 100 Angstroms (10-sm) have increased stability.
• condensable hydrocarbons for example C 4 or higher than C 4
• the preferred supports usually have a specific surface of approximately 20 to 300 m 2 X g-1, these values not being limiting.
• a copper compound other than a sulfide
• a solid mineral support or dispersant can be carried out by any method known to a person skilled in the art, for example by mixing with a copper compound or by impregnation using a solution of a copper compound.
• the commonly used copper compounds are compounds which can be easily transformed into copper oxide at relatively low temperatures.
• copper oxides copper hydroxide Cu (OH) 2
• basic copper salts in particular carbonates of the formulas CuCO 3 , Cu (OH) 2 and 2CuCO 3 , Cu (OH) 2
• salts and organic complexes of copper such as salts of carboxylic acids, for example formates, acetates, tartrates, citrates, benzoates, oxalates, malonates, succinates, glycolates, lactates and acetylacetonate; and copper nitrate.
• the copper compound it is usually preferred to introduce the copper compound by impregnating the support using an aqueous or organic solution of a copper compound and preferably using an aqueous solution of a copper compound.
• an aqueous solution of copper nitrate is used.
• a small proportion of a soluble silver compound can optionally be introduced onto the support.
• the amount of silver introduced into the support expressed in weight of silver relative to the support usually represents from 0 to 5% by weight.
• Other metals may also possibly be present, for example iron, lead.
• the solid mineral support or dispersant comprising a copper compound, other than a sulphide is then optionally calcined so as to transform, at least in part, the copper compound into copper oxide.
• this calcination step may not be necessary.
• the operating conditions are preferably chosen so as to transform at least most of it, that is to say at least 50%, and preferably at least 80% and very advantageously 100% of the compound of copper present in copper oxide (CuO).
• Calcination can be carried out in a neutral or oxidizing atmosphere. It is thus possible to operate in the presence of an inert gas such as nitrogen, argon, helium or a mixture of these gases. It is also possible to operate in the presence of a mixture of oxygen and inert gas containing for example from 1 to 60% by weight of oxygen or even in the presence of substantially pure oxygen.
• the calcination is preferably carried out in an oxidizing atmosphere and air is advantageously used, but it is also possible to use air enriched with oxygen.
• the calcination temperature is usually about 200 to about 1000 ° C and preferably about 300 to about 800 ° C and preferably about 350 to about 600 ° C.
• Calcination can be carried out in a static atmosphere or under a stream of gas. It is usually preferred to operate under a gas stream, and an air stream is advantageously used.
• the hourly space velocity (VVH) expressed in volume of gas per volume of capture mass and per hour is usually about 0 to about 20,000 h- 1 and preferably about 100 to 10,000 h- 1 and often about 300 to 5000 h- 1 ,
• the duration of this calcination step is usually from about 0.5 hour to about 24 hours and preferably from about 0.5 hour to about 12 hours and preferably from about 1 hour to about 10 hours.
• step (c) The product usually containing copper oxide from step (a) or from step (b) of calcination is then brought into contact with at least one organic polysulfide so as to incorporate, at least partially, this sulfide compound or agent with solid mineral support or dispersant, pro duit resulting from this incorporation (step (c)) constituting the precursor of the mercury capture mass of the present invention.
• the sulfiding agent used in the process of the present invention is an organic polysulfide of general formula RS ( n ) -R 'in which n represents an integer from 2 to 20, preferably from 3 to 20 and often from 3 to 8 and more particularly from 4 to 7; R and R 'each represent an identical or different organic radical containing from 1 to 150 carbon atoms, preferably from 10 to 60 carbon atoms, that is to say from 5 to 40 carbon atoms and more particularly from 7 to 16 carbon atoms , these radicals usually being chosen from the group consisting of saturated or unsaturated, linear or branched or naphthenic alkyl radicals, aryl radicals, alkylaryl radicals and arylalkyl radicals, these various radicals possibly comprising at least one hetero atom; R optionally can also be a hydrogen atom.
• the incorporation of the organic polysulfide is usually carried out at a temperature below about 100 ° C, usually from about 0 to 50 ° C and preferably from about 10 to 35 ° C and for example at room temperature (usually around from 20 ° C or 15 ° C to 25 ° C).
• Polysulfide is usually used in solution in a suitable organic solvent, which depends in particular on its nature. This solvent can be an ether, an ester, a ketone, a hydrocarbon or a mixture of two or more of these compounds.
• This product is marketed for example by the company Elf Aquitaine under the name TPS 32, in particular because it contains approximately 32% by weight of sulfur.
• This product is marketed by the company Elf Aquitaine under the name TPS 37, in particular because it contains about 37% by weight of sulfur or by the company PENWALT under the name of TNPS.
• the quantity of polysulphide which is incorporated into the absorption mass is suitably chosen to subsequently allow the transformation of the copper compounds contained in said mass at least in part into copper sulphide.
• the amount of polysulfide can easily be adjusted depending on the amount of copper sulfide that is desired.
• the quantity of organic polysulphide used, calculated in sulfur atoms, is advantageously such that the sulfur atomic ratio on metals present in the mass, is approximately 0.7: 1 to 1.2: 1 and preferably approximately 0 , 8: 1 to 1.1: 1.
• step (c) of incorporation of a sulfurization agent into the solid mineral support or dispersant is then subjected to a heat treatment in a non-oxidizing atmosphere, for example neutral or reducing and preferably neutral, under scanning of gas, at a temperature and for a time sufficient to allow the formation of sulphide of the metal or metals present.
• a non-oxidizing atmosphere for example neutral or reducing and preferably neutral
• This heat treatment is usually carried out under a stream of inert gas, for example nitrogen, argon, helium, water vapor or a mixture of two or more of these gases.
• inert gas for example nitrogen, argon, helium, water vapor or a mixture of two or more of these gases.
• a gas containing water vapor and at least one other inert gas such as nitrogen, argon and helium is used.
• the amount of water vapor in the gas mixture then advantageously represents at least 50% by weight relative to the weight of the mixture. It is often preferable to use steam alone, not diluted by another inert gas.
• the absorption mass containing the organic polysulphide is treated under a stream of gas preferably containing water vapor, at a temperature of about 100 to about 250 ° C. , preferably approximately 110 to 180 ° C and often approximately 120 to 150 ° C, with an hourly space velocity (VVH) expressed in volume of gas per volume of capture mass and per hour of approximately 100 to 10,000 h- 1 , preferably around 300 to 5000 h- 1 and often around 500 to 2000 h- 1 .
• VVH hourly space velocity
• the duration of this gas sweeping treatment is usually from about 1/2 hour to about 24 hours and preferably from about 1/2 hour to about 10 hours, with a duration of about 2 hours usually being sufficient.
• Another advantageous form of this heat treatment consists in carrying out a first part of this step under a stream of inert gas containing substantially no water vapor (for example less than 5% by weight and preferably less than 1% by weight ) usually chosen from the group formed by nitrogen, argon, helium and a mixture of two or more of these gases, at a temperature and for a duration chosen from the ranges given above, then to be carried out in a second part of this step a treatment in the presence of an inert gas containing water vapor (usually at least 25% by weight and preferably at least 50% by weight and sometimes advantageously 100% by weight) under the conditions mentioned above.
• inert gas containing substantially no water vapor usually chosen from the group formed by nitrogen, argon, helium and a mixture of two or more of these gases
• the absorption mass can optionally be dried, preferably under a stream of inert gas, for example under a stream of nitrogen, helium, argon or a mixture of two or more of these gases, then optionally cooled to room temperature preferably in the presence of the above-mentioned gas stream, before being brought into contact with the fluid to be purified.
• a stream of inert gas for example under a stream of nitrogen, helium, argon or a mixture of two or more of these gases
• the weight of copper sulfide, expressed as copper, contained in the mass is usually about 2 to 65%, preferably about 5 to 50% of the weight of the mass; in an often advantageous form, masses are used containing an amount of copper sulfide, expressed as copper, representing approximately 10 to 50% of the weight of the mass and sometimes approximately 20 to 50% of this weight. Masses are usually preferred, at least 30% and preferably at least 80% of the copper being in the sulphide state.
• the mercury capture masses obtained by the process of the present invention can be used to purify gases or liquids containing mercury. These solid masses are usually used in the form of a fixed bed through which the fluid to be purified is passed.
• the temperature range where the capture masses are effective is usually between approximately minus 50 ° C and plus 200 ° C. In the case of air demercurization it is however preferable to work at a temperature below approximately 100 ° C.
• the capture of mercury can be carried out at atmospheric pressure or under a lower or higher pressure, the total pressure possibly reaching for example 20 MPa.
• the VVH for gaseous charges is usually around 500 to 5000 h- 1 , but one preferably operates at a VVH of around 2000 to 20000 h- 1 and advantageouslyfrom about 4,000 to 20,000 h- 1 ; for liquid loads the VVH will preferably be around 0.1 to 50 h -1 .
• the fluids treated can contain, for example, from 10 nanograms to 2 grams of mercury or more, per cubic meter.
• the gases treated are most often hydrocarbons or mixtures of hydrocarbons such as, for example, natural gases containing a major proportion of methane and a minor proportion of C 2 and / or higher hydrocarbons and mercury.
• the treated gas can also be hydrogen, such as for example electrolytic hydrogen; it can also be air provided that it operates under conditions of temperature and / or pressure such that contact with this gas does not cause the absorption mass or an excessive part of said gas to oxidize mass. It is also possible to envisage the treatment of mixtures containing several of the compounds or gases mentioned above.
• the liquids treated are most often mixtures of hydrocarbons usually containing a major proportion of saturated hydrocarbons having 5 to 10 carbon atoms in their molecule and a minor proportion of heavier hydrocarbons, having more than 10 carbon atoms in their molecule, and mercury.
• the mercury removal device can for example consist of a single reactor or of at least two reactors in parallel, but at least two reactors are preferably used in series.
• the present invention also relates to a process for the regeneration of a solid mass for absorbing mercury containing an inorganic support and copper at least partly in the sulphide state.
• the present invention relates more particularly to a process for regenerating the solid masses for absorbing mercury used for the elimination of mercury present in a fluid (gas or liquid).
• absorption masses to which the regeneration process of the present invention applies are for example prepared according to the process described above or by any other method known to those skilled in the art.
• Document US-A-4094777 discloses a process for regenerating solid masses for absorbing mercury, consisting in heating an absorption mass whose efficiency is no longer, for example, more than 70% its initial effectiveness, with sweeping by an oxidizing, neutral or reducing gas, by example with sweeping of air, methane or hydrogen, preferably for 0.1 to 48 hours at a temperature of 200 to 500 ° C. Heating is, if necessary, followed by resulfurization of the mass obtained, using a gaseous sulfiding agent such as hydrogen sulfide or using a solution of a sulfide in water or in an organic solvent, for example an aqueous solution of sodium sulfide , potassium sulfide or ammonium sulfide.
• a gaseous sulfiding agent such as hydrogen sulfide or using a solution of a sulfide in water or in an organic solvent, for example an aqueous solution of sodium sulfide , potassium sul
• the sulfurization method using hydrogen sulfide usually requires working at relatively high temperatures, sometimes above 200 ° C; moreover, this compound is toxic and smelly, and the time necessary for the sulfurization is usually several hours and sometimes even several days.
• sulfide solutions especially aqueous sulfide solutions, for example aqueous ammonium sulfide solutions, usually makes it possible to work at relatively low temperatures, for example below 100 ° C.
• aqueous sulfide solutions for example aqueous ammonium sulfide solutions
• ammonium sulfide is a toxic and easily decomposable compound, which complicates its use.
• the absorption masses regenerated by the process of the present invention find practically an absorption efficiency of mercury very close to those of new masses, that is to say masses having no not yet come into contact with a liquid or gas containing mercury.
• the absorption mass must contain copper sulfide.
• the amount of copper sulfide contained in the absorption mass, expressed as copper usually represents from 2 to 65%, preferably from approximately 5 to 50% of the weight of the mass; in an often advantageous form, masses are used containing an amount of copper sulfide, expressed as copper, representing approximately 10 to 50% of the weight of the mass and sometimes approximately 20 to 50% of this weight.
• the mercury capture masses, containing copper sulphide have a capture efficiency which evolves over time as they capture the mercury contained in the fluid in contact with which they are brought.
• the capture efficiency decreases and it becomes necessary, either to use another new solid mass, or to regenerate the solid mass whose capture efficiency has become insufficient.
• regeneration is carried out when the capture efficiency is no more than 40 to 99.8% and preferably 50 to 99.5% of the initial efficiency and most preferably from 70 to 99 % of its initial efficiency.
• the capture efficiency decreases notably and sometimes rapidly, for example when these masses are brought into contact with an oxidizing atmosphere, and that, for example, as a result of an involuntary modification of the contact conditions, a an exothermic reaction takes place causing rapid degradation of the efficiency of capture of said mass.
• the regeneration method of the present invention comprises bringing the absorption mass having at least partially lost its mercury capture efficiency, previously rid of at least most of the mercury it contains, with at least one agent of sulfurization, so as to at least partially incorporate this agent into said absorption mass, preferably at least partially in its porosity, said sulfurization agent being an organic polysulfide of general formula: in which n represents an integer from 2 to 20, preferably from 3 to 20, and often from 3 to 8 and more particularly from 4 to 7; R and R 'each represent an identical or different organic radical
• radicals usually being chosen from the group consisting of saturated or unsaturated, linear or branched or naphthenic alkyl radicals, aryl radicals, alkylaryl radicals and arylalkyl radicals, these various radicals possibly comprising at least one hetero atom; R optionally can also be a hydrogen atom.
• the incorporation of the organic polysulfide is usually carried out at a temperature below 100 ° C, usually from about 0 to 50 ° C and preferably from about 10 to 35 ° C and for example at room temperature (usually around 20 ° C or 15 ° C to 25 ° C).
• Polysulfide is usually used in solution in a suitable organic solvent, which depends in particular on its nature. This solvent can be an ether, an ester, a ketone, a hydrocarbon or a mixture of two or more of these compounds.
• This product is marketed for example by the company Elf Aquitaine under the name TPS 32, in particular because it contains approximately 32% by weight of sulfur.
• This product is marketed by the company Elf Aquitaine under the name TPS 37, in particular because it contains about 37% by weight of sulfur or by the company PENWALT under the name of TNPS.
• the quantity of polysulphide which is incorporated into the absorption mass is suitably chosen to subsequently allow the transformation of the copper compounds contained in said mass, at least in part, into copper sulphide.
• the amount of polysulfide can easily be adjusted depending on the amount of copper sulfide that is desired.
• the quantity of organic polysulphide used, calculated in sulfur atoms is advantageously such that the sulfur atomic ratio on metals present in the mass is approximately 0.7: 1 to 1.2: 1 and preferably approximately 0, 8: 1 to 1.1: 1.
• the step of incorporating the organic polysulfide into the absorption mass is preferably followed by a treatment in a non-oxidizing atmosphere, for example neutral or reducing, and preferably neutral, under gas sweeping, at a temperature and for a sufficient time to allow the sulfide formation of the metal (s) present.
• This treatment is usually carried out under a stream of inert gas, for example nitrogen, argon, helium, water vapor or a mixture of two or more of these gases.
• a gas containing water vapor and at least one other inert gas such as nitrogen, argon and helium is used.
• the amount of water vapor in the gas mixture then advantageously represents at least 50% by weight relative to the weight of the mixture. It is often preferable to use steam alone, not diluted by another inert gas.
• the absorption mass containing the organic polysulphide is treated under a stream of gas preferably containing water vapor, at a temperature of approximately 100 to approximately 250 ° C., preferably approximately 110 to 180 ° C and often approximately 120 to 150 ° C, with an hourly space velocity (VVH) expressed in volume of gas per volume of capture mass and per hour of approximately 100 to 1000 h-1 , preferably from about 300 to 5000 h- 1 and often from about 500 to 2000 h- 1 .
• VVH hourly space velocity
• the duration of this gas sweeping treatment is usually from about 1/2 hour to about 24 hours and preferably from about 1/2 hour to about 10 hours, with a duration of about 2 hours usually being sufficient.
• Another advantageous form of this heat treatment consists in carrying out a first part of this step under a stream of inert gas containing substantially no water vapor (for example less than 5% by weight and preferably less than 1% by weight ) usually chosen from the group formed by nitrogen, argon, helium and a mixture of two or more of these gases, at a temperature and for a duration chosen from the ranges given above, then to be carried out in a second part of this step a treatment in the presence of an inert gas containing water vapor (usually at at least 25% by weight, and preferably at least 50% by weight and sometimes advantageously 100% by weight) under the conditions mentioned above.
• inert gas containing substantially no water vapor usually chosen from the group formed by nitrogen, argon, helium and a mixture of two or more of these gases
• the absorption mass can optionally be dried, preferably under a stream of inert gas, for example under a stream of nitrogen, helium, argon or a mixture of these gases, then optionally cooled to room temperature, preferably in the presence of the above-mentioned gas stream, before being brought back into contact with the fluid to be purified.
• a stream of inert gas for example under a stream of nitrogen, helium, argon or a mixture of these gases
• the absorption mass is first freed at least in part of the mercury which it contains by any means well known to those skilled in the art.
• This removal of mercury can advantageously be carried out by a heat treatment in an oxidizing atmosphere, for example under a stream of air or of a mixture of oxygen and inert gas containing for example from 1 to 60% by weight of oxygen. It is also possible to use oxygen-enriched air. For practical reasons, air is advantageously used.
• the temperature of this treatment in an oxidizing atmosphere is usually about 300 to 800 ° C. and preferably about 400 to 600 ° C.
• This treatment makes it possible to recover the mercury and to obtain a solid absorption mass, preferably rid of at least most and very advantageously all of the mercury.
• This treatment has the consequence of transforming the absorption mass into an inactive mass for the absorption of mercury, in particular as a result of the at least partial transformation of copper into copper oxide (CuO) inactive for the capture of mercury.
• the inactive mass obtained is however easily regenerable by the process of the present invention.
• the cycle thus described comprising a mercury capture period, a regeneration period, then a new mercury capture period can be repeated several times.
• the absorption masses are preferably used in the form of a fixed bed through which the gas or the liquid to be purified is passed.
• the absorption masses are regenerated according to the process of the present invention preferably in a unit specially designed to carry out this regeneration. However, it is possible to regenerate the capture mass in the reactor used for the treatment of the fluid.
• the alumina beads thus impregnated are dried and calcined for 7 hours at 430 ° C. under a stream of air at a VVH of 5000 h -1 .
• the beads thus obtained are in a second step impregnated with a bezel, using 1 I of an aqueous solution at 20% by weight of ammonium sulfide.
• the excess sulfur is removed by drying in an oven at 150 ° C for 18 hours under a stream of nitrogen (VVH of 5000 h-1).
• the mass A obtained contains copper sulphide in an amount expressed by weight of copper of 20% relative to the weight of the mass.
• X-ray diffraction analysis indicates that all of the copper is in the form of copper sulfide.
• the alumina beads thus impregnated are dried and calcined for 7 hours at 430 ° C. under a stream of air at a VVH of 5000 h -1.
• the beads thus obtained are in a second step impregnated with a bezel, by means of 1 I of an aqueous solution at about 20% by weight of sodium sulfide.
• the excess sulfur is removed by drying in an oven at 150 ° C for 18 hours under a stream of nitrogen (VVH of 5000 h-1).
• the mass B obtained contains copper sulphide in an amount expressed by weight of copper of 20% relative to the weight of the mass.
• X-ray diffraction analysis indicates that all of the copper is in the form of copper sulfide.
• alumina beads of 50 m 2 x g-1 of specific surface and pore volume 1.2 cm3 x g- 1 per 1.2 I of an aqueous solution containing 770 g of copper nitrate trihydrate .
• the alumina beads thus impregnated are dried and calcined for 7 hours at 430 ° C. under a stream of air at a VVH of 5000 h-1.
• the calcined beads obtained above are impregnated at a temperature of 20 ° C. with 0.86 I of a solution at 30% by weight of ditertiononylpolysulfide (product marketed by the company Elf-Aquitaine under the name TPS 37) in the "White-Spirit".
• the volume of solution used corresponds to the impregnation volume of the mass treated, so that all of the polysulphide is absorbed in said mass.
• X-ray diffraction analysis indicates that all of the copper is in the form of copper sulfide.
• the amount of copper sulphide expressed by weight of copper is 20% relative to the weight of the mass.
• the calcined beads obtained above are impregnated at a temperature of 20 ° C. with 0.90 liters of a solution at 30% by weight of ditertiododecylpolysulphide (product sold by the company Elf-Aquitaine under the name TPS 32) in the "White-Spirit".
• the volume of solution used corresponds to the impregnation volume of the mass treated, so that all of the polysulfide is absorbed in said mass.
• X-ray diffraction analysis indicates that all of the copper is in the form of copper sulfide.
• the amount of copper sulphide expressed by weight of copper is 20% relative to the weight of the mass.
• a mass E is prepared as described above in Example 3 from the same alumina beads.
• the preparation process is identical in all respects except that the alumina beads are impregnated with a solution containing 760 g of copper nitrate trihydrate and 7 g of silver nitrate.
• X-ray diffraction analysis shows that all of the copper and all of the silver in mass E is in the form of sulfide.
• a mass F is prepared as described in Example 3 from the same alumina beads.
• the preparation process is identical in all respects except for the fact that the alumina beads are impregnated with an aqueous solution containing 490 g of precipitated copper carbonate 2C U C0 3 , Cu (OH) 2 .
• X-ray diffraction analysis shows that all of the copper is in the form of copper sulfide.
• the amount of copper sulphide expressed by weight of copper is 20% relative to the weight of the mass.
• a mass G is prepared as described in Example 4 from the same alumina beads.
• the preparation process is identical in all respects except that the alumina beads are im pregnated with an aqueous solution containing 490 g of precipitated copper carbonate 2CuCO 3 , Cu (OH) 2 .
• X-ray diffraction analysis shows that all of the copper is in the form of copper sulfide.
• the amount of copper sulphide expressed by weight of copper is 20% relative to the weight of the mass.
• a mass H is prepared as described in Example 3 from the same alumina beads.
• the preparation process is identical in all respects except that the alumina beads are impregnated with a solution containing 480 g of precipitated copper carbon 2CuCO 3 , Cu (OH) 2 and 7 g of silver nitrate .
• the mercury capture masses A to H obtained in the previous examples are tested under the following conditions.
• the apparatus consists of a tubular metal reactor whose inactivity for fixing mercury has been controlled. 30 ml of the capture mass to be tested are introduced into this reactor and a stream of natural gas containing mercury is passed through at a temperature of 70 ° C., under a pressure of 35 bars (3.5 MPa) at a VVH of 15,000 h- 1 (TPN, temperature and normal pressure), i.e. a flow rate of 450 I x h-1.
• TPN temperature and normal pressure
• the centesimal volume composition of the natural gas to be purified is 84% CH 4 , 0.6% hydrocarbons having 5 and more carbon atoms in their molecule, the rest being made up of a mixture of N 2 , C0 2 , C 2 H 4 , CaHa and C 4 H l o.
• the mercury content in the gas entering the reactor is 2 x 10-5 g / m3 (TPN).
• the quantity of mercury remaining in the gases after purification is evaluated by a method using the principle of the variation of resistivity of a film of gold amalgamated by mercury.
• a measurement is then carried out after 500 hours of operation under the conditions described above.
• the quantity of mercury remaining in the gas after purification is evaluated by a method using the principle of the variation of resistivity of a gold film amalgamated by mercury.
• the deactivation as a function of time is determined by means of a measurement after 500 hours of operation under the conditions described above.
• An accelerated aging test is also carried out, then, as follows: after 500 hours of collection under the conditions described above, a gas of identical composition but containing 20 mg / m 3 of mercury is passed over 200 hours (which is equivalent to 200,000 hours of operation under the above conditions with a gas containing 2 x 10-5 g / m 3 of mercury).
• Example 2 30 ml of mass A prepared according to the method described in Example 1 are placed in a reactor identical to that described in Example 10, in which a stream of dry air (polluted by mercury) at a temperature of 70 ° C, at a pressure of 35 bar (3.5 MPa) at a VVH of 15,000 h-1.
• the dry air to be purified contains 2 x 10-5 g / m 3 of mercury.
• mass K The mass thus regenerated, called mass K, is tested under the same conditions as those described in Example 10.
• a mass 1 obtained by following the process described in Example 10 is regenerated according to a process identical to that described for the preparation of mass A, that is to say by impregnation with an aqueous solution of sulfide d 'ammonium.
• mass L The mass thus regenerated, called mass L, is tested under the same conditions as those described in Example 10.
• a mass 1 obtained by following the process described in Example 10 is regenerated by impregnation using a 20% by weight aqueous solution of sodium sulfide.
• mass M The mass thus regenerated, called mass M, is tested under the same conditions as those described in Example 10.
• a mass J obtained according to the process of example 11 is regenerated according to the method described in example 12.
• the mass thus regenerated called mass N is tested under the same conditions as those mentioned in example 11. The test is continued without incident for 260 hours.
• a mass J obtained according to the process of example 11 is regenerated according to the method described in example 13.
• the mass thus regenerated called mass O is tested under the same conditions as those mentioned in example 11. The test is continued without incident for 260 hours.
• a mass J obtained according to the process of example 11 is regenerated according to the method described in example 14.
• the mass thus regenerated called mass P is tested under the same conditions as those mentioned in example 11. The test is continued without incident for 260 hours.
• mass S 100 g of a mass J obtained according to the process of example 11 are regenerated according to the technique described in example 18.
• the mass thus regenerated called mass S is tested under the same conditions as those mentioned in example 11. The test is continued without incident for 260 hours.
• the efficiency of the masses K, L and M obtained by regeneration of the mass 1 according to the methods of the prior art is lower than that of the masses Q and R obtained by regeneration of the mass 1 according to the present invention. It is the same for the efficiency of the masses N, O and P regenerated from the mass J according to the techniques of the prior art, that is less than that of the masses E and F obtained by regeneration of the mass J according to the present invention.
• the masses K, L and M n no longer have sufficient efficiency from the industrial point of view, while the efficiency of the masses Q and R is unchanged compared to their initial efficiency.

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• 1988
  • 1988-05-22 DZ DZ880065A patent/DZ1209A1/fr active
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